Catalytic conversion of hydrocarbons with mixed catalysts



July 4, 1944. A. RS.WORKMAN CATALYTIC CONVERSION OF HYDROGARBONS WITH MIXDZCATALYSTS Filed Dec. 4, 1941 mmv] amjoou hat@ LIED VSOP Dumb.

INVENTOR ARNOLD R. WORKMAN m :ATTORNEY num silicates with certain metal oxides.

sr'rs rifas l est CATALYZ'EHC CONVERSION @F HOGAR@ BUNS WTH @'EALYSTS molan-Workman, Malverne, N.' Y., assigner to Cities Service Oil-Company, New York, N. Y., a corporation of Pennsylvania Application Becember d, 11.941, Serial No.l 23,563

7 Claims.

This invention relates to an improved catalytic process for the` conversion of hydrocarbons of low antiknock characteristics into hydrocarbons having high antilmccl; properties suitable for aviation fuel. More particularly, the invention relates to the catalytic conversion of hydrocarbons by the use of a mixed catalyst or a mixture of catalysts. The catalytic conversion processes employed at the present time for the most part involve the use of inorganic catalytic materials consisting of various clays or especially prepared inorganic catalysts comprising mixtures of alumi- The fixed bed type of catalytic process usually involves the use of a preformed catalyst while the processes employing clays usually involve the use oi a powdered clay or similar materia1.

One of the most important disadvantages ci the lpresent catalytic processes is the carbonization of the catalyst and its consequent deactivation and loss of eectiveness. In many instances the pores of the catalytic material are carbonized over and active surfaces are completely covered with a carbonaceous nlm. All processes there# fore include the necessary elaborate provisions for burning out the carbonaceous deposit on the catalyst. Fixed catalyst beds are used for only a few minutes before they-must be burned out, and in processes Where the catalyst is suspended in the oil being cracked or converted the catalyst is almost always subjected to a burning operation :before it is returned to the process. This latter burning procedure' involves the handling of hundreds of tons of material daily in processes which include the use of from 400% to 500%y of catalyst. Where such large proportions of the catalyst is used however, the percentage of carbonaceous deposit may amount to only 2% or 3%. However, in all known cases the catalyst is burned for revivication on every cycle.

The primary object of the present invention .is to provide an improved catalytic process for converting hydrocarbon oils into high antiknock ,gasoline in which the objectionable carbonaceousdeposit is greatly reduced and minimized.

(ci. is i procedure in which a mlnedcatalyst is employed for effecting the conversion.

Accordingly, the improved'process of the pres?V ent invention comprises a relatively low pressure and low temperature catalytic conversion process in which a low 'antilmocir hydrocarbon is mixed with a preheated active catalytic mixture comprising a substantial proportion of activated carbon and a substantial proportion of an inorganic catalyst oi the clay type, subjecting the resultmg mixture, with the cutanei in powdered form and in suspension, to a reaction temperature adapted to dehydrogenate and crack the hydrocarbon and at the same time eiect polymerization, rearrangement and alkylation of the constituents to .form hmh anti-knock products.

The improved'process preferably includes other features such. as the simultaneous or independent conversion of light distillate feed stocks such as Ca and C4 hydrocarbons. the use oirsuch materials for suspending and preheatins the catalyst and the recovery of C: and C4 oleiins for use in the process. The process also preferably includes the use of a low pressure. absorption operation for eliminating Cal and lower gaseous constituents fromthe conversion products, the separation of the carbon catalyst from the inorganic catalyst together with their separate regeneration and of'two or moreoi' these stocks. is introduced into A further object of the invention is to avoid a n l hydrocarbons of low antiknock value into hydrocarbons of high antiknock value by a. combined 'dehydrogenatiom polymerization and alkylation 55 F. to 960 F. The heating of the oil stock, 'for l example, gas oil, in the pipe still heater 8 is only suliicient to vaporize the stock and bring'it to the temperature'referred to. 'I'he highly heated vapors are conducted from the heater 6 into a line I and intimately mingled with a powdered catalyst comprising a. mixture of from 10% to 40% oi activated carbon or charcoal and from 90% to 60% of an activated inorganic catalyst of the clay type in a mixer I0, the catalyst being supplied from a hopper I2 through a line I4 containing a catalyst pump as shown. The oil vapors and mingled catalyst preferably in proportions of about 1 to 1 by weight, are conducted through a reaction furnace I6 in which the mixture is merely maintained at alreaction temperature of from 885 to about 970 F. for a period of from three to ten minutes. The percentage of catalyst may be as low as 10% by Weight.

The conversion products containing the suspended catalyst are conducted from the pipe still heater I6 through a transfer line I8 and passedinto the first of a series of cyclone separators 20 and 22 which are adapted to separate most if not all of the catalytic materials from the hydrocarbon vapors. The major part of the catalytic material will be separated in the cyclone separator 20 while the vapors and the remainder of thecatalyst passes on through vapor line 24 to the second separator 22 for further separation. The partially spent catalyst separated out in the elements 20y and 22 passes through a line 26 to apparatus for effecting the separation between the carbon and the inorganic catalyst designatedv generally at 28. y

The separation of the two catalytic materials in the apparatus 28 is done so that these materials can be more effectively revivied. for reuse in theA process. The separation of the carbon catalyst from the inorganic clay type catalyst may be accomplished by well-known means such as classifiers, precipitators or filters, for example the carbon catalyst separates readily from the clay type catalyst in a coal-washing machine by passing the catalyst mixture with water through the machine in which the clay settles out first and the carbon floats off and is separately co1- lected. In this operation the separated materials are collected in lter presses, dried and sent to the respective regenerating apparatus 32' and 36. Coal-washing machines operate on the principle of the Spitzkasten which consists of a series of conical boxes in which each succeeding box is larger and deeper than the rst. In addition to the water passed into such a machine with the materials to be separated, a stream of water is also preferably introduced into the apex of each box to effect a sharper classication. The catalytic materials may also be separated by well-'known electric separators because the carbon is an electrical conductorl while the clay is not. The inorganic catalyst separated by the apparatus 28 is conducted from the apparatus 28 through a line 30 to apparatus 32 for regeneration, while the separated carbon catalyst is conducted through a line 34 to an apparatus 36 for regenerating the carbon catalyst. `Well.-known apparatus and methods may be used for reactivating both catalysts. The inorganic, claytype catalyst may be reactivated in the appa- .ratus 32 at temperatures of about 1100 F. or slightly lower by intimate contact with air or oxygen to the extent of about of that required for burning` out carbonaceous material and reactivating the catalyst. Sometimes a .small amount of steam is required along with the air unless the air itself is sufficiently humid. The carbon catalyst'in the apparatus 36 may be reactivated at temperatures of from 1100 to 1250 F. oy intimately. contacting the carbon catalyst with superheated steam, care being taken to avoid substantial oxidation of the carbon.

apparat'us 28 and reactivated in the apparatus 32 and 36 on each cycle, but may be substantially regenerated together alt temperatures of about 1150 F. by intimate contact with a relatively small proportion of superheated steam. Such revivified catalyst mixture may be sent directly to the hopper I2 or utilized in a. manner described hereinafter. Separation of the carbon catalyst from the inorganic catalyst in the apparatus 28 is primarily for the purpose of separately regenerating the inorganic catalyst which is necessary in many cases only periodically. The

presence of a relatively large proportion of the activated carbon catalyst along with the activated inorganic catalyst during the conversion operation appears to inhibit carbon formation and to substantially avoid carbonization of the inorganic catalyst, which is one of the chief processes using inorganic catalytic materials exclusively. The catalyst is preferably supplied hot and dry to a dry oil vapor to be converted.

The conversion products resulting from the catalytic conversion in the pipe still heater I 6,

in vapor form and free of catalytic material, orv

substantially so, are conducted from the cyclone separator 22 through a vapor line 38 into a mixing nozzle 40 in which the vapors are cooled to a 'substantially low temperature by the introduction of relatively cool feed stock such as gas oil or kerosene introduced into the nozzle 46 through a line 42. The resulting chilled products at a temperature of from 150 to 250 F. are conducted through a line 44, and a cooler therein, into the lower portion of a lowv pressure absorber 46. The pressure in the absorber 46 is preferably only about 10 lbs. pe'r square inch and is maintained by a valve in the dry gas discharge line at the top of the absorber. The pressures in the preceding parts of the apparatus including the cyclone separators and the pipe still heaterl6 are as low as possible consistent with the maintenance of ow and the back-pressure of fabout 10 lbs. per square inch in the absorber 46.

The liquid, vapor and Igaseous constituentsintroduced into the absorber through the line 44 are preferably at a temperature of vapproximately to 100 F. At the same time an absorption oil such as a. gas oil distillate or other feed stock, higher boiling than gasoline, is introduced into the top of the absorber through a line 46, in sufllcient quantity to absorb substantially all of the C3 and higher molecular weight hydrocarbons. The liquid constituents introduced into the bottom of the absorber 46 from the line 44 pass into a settling section in which any solid particles of the` catalyst are collected and removed with a portion of the oil through a valved line 50. However, the major portion of this liquid material overflows into a trap 52 where it is collected alongwith the absorption oil and the constituents absorbed in the absorber withdrawn through a line 64 having a pump therein, and forced at a pressure of about 250 lbs. per square inch through the heating coil of a pipe still heater 56 for the purpose of heating the oil mixture to a temperature suilicient to fractiona-te out the gasoline and other hydrocarbons up to and including gas-oil constituents, the heated products Abeing conducted through a transfer line Il into the lower'portion of a. fractionating tower 66.

The oil removed through line 50 maybe freed,

assedio of catalyst, as by hltration and then introduced /into the line et.

The fractionation carried out in the tower d@ is preferably conducted in sucha i f.; er that the residual constituents of higher boiling point than gas oil are removed through a valved line 02. while end point gasoline constituents and lower boilingr materials including the Cs hydro carbons are removed overhead through a vapor line @it and 'introduced into the midportion of a stabilizer tower 65. The intermediate boiling constituents comprising gas-oil and kerosene boiling range hydrocarbons may be withdrawn as a side streA into line i which connects directly with the pipe still heater t. The fractionation in the tower tti may be controlled by cooling the top'oi the tower to produce the desired amount of refluxing. 'The side stream withdrawn through the valvedrline t may be usedv as charging stock for the pipe still furnace 6, or any portion or all of this side stream may -be used as absorption oil inthe absorber d@ by conducting it through a valved line 63 and a cooler therein directly into the line td. A portion of the side stream in line 63, cooled or not, may be used in line d2.

The vapors introduced into the stabilizer tower I et are fractionated therein at a pressure o about 175 ibs. vper square inch to produce a bottoms product comprising a stabilized end point gasoline which is removed through a reboiler and dis-` charged through a valved line l0. The vapors produced in the stabilizer are taken overhead through a vapor 1ine`l2, subjected to condensing conditions, and the resulting condensate collected in a receiver M, from which a portion may be returned to the top of the stabilizer'to provide the desired reiluxing conditions. The

vapors in the line l2 comprise the butano in excess of that required in the gasoline product, isobutane, butylene, propylene and propane. Most of these constituents may be condensed and the uncondensed gas discharged from the system,

but the whole mixture, which contains very little is placed under a pressure of about 500 lbs. per

square inch by means ci a. pump or compressor 80, -and a portion of the mixture conducted into a mixing nozzle 82 which is supplied with activated inorganic catalyst from lthe regeneration appa-- ratus 32 through a valved supply line 04. Another portion, of the stock in the line i6 is conducted through a valved branch line 30 into a mixing nozzle 8,8 while activated carbon catalyst from the apparatus 35 is supplied thereto 'through a valved supply line 90.

The catalyticy materials introduced into Vthe I in which me mixture is heated rapidly to a temline 0d to the high temperature vapors from the .pipe still heater d may replace all or a part oi the catalyst initially supplied through the line iii. The hopper li therefore may -be used only in starting up the apparatus or ier supplying a small proportion of fresh catalyst mixture to the system. Fresh catalyst however may be supplied to either or both of the mixers 52 and 08, and catalytic material may be recycled to these mix- I ers directly from the line 26. The catalyst from the line 2d however is preferably regenerated in apparatus such asl the apparatus 3d, with superheated steam, without burning any of the carbon. it intervals, however, the inorganic catalyst is preferably separated out and regenerated in the apparatus B2 in the manner described above. An insulated reaction chamber may be used in place of, or along with the reaction heater le, the reactiomtime however being preferably about live minutes for gas oil, kerosene and naphtha stocks.

While the light stock supplied through the line 'it and used as a catalyst carrier for supplying the catalyst in a highly heated serated condi# itori to the process is advantageous, a preferred form ofthe process includes the simultaneous conversion, polymerization andalkylation of the stool: heated in the pipe still furnace d with the light stock supplied through the line l0. In such an operation the C3 and C4' hydrocarbon mixture obtained from the receiver M and containing approximately'65% of olen hydrocarbons, is supplied through the line i6 to pick up the inorganic catalyst and carbon catalyst to produce a rather concentrated suspension or aerated mixture in the line td. This suspended catalyst and light stock is heated to a temperature oi' from 860 to 970 F. in the pipe still heater @Sjwhile a gasoil Atype feed stock is simultaneously heated to approximately the same temperature in the pipe still heater d. The transfer line products from the two heaters are intimately mixed in the mixer 99 after which the whole mixture at re' action temperature and containing about by weight oi the catalyst mixture is reacted in the pipe still heater IB for a. period of about seven minutes. The activated carbon catalyst in the presence of the clay, in this operation, dehydrogenates the gas oil constituents and thereby promotes cracking, while the clay type'catalyst.

in the presence of the activated carbon promotes polymerization and alkylation reactions, so that the light hydrocarbons supplied through the line 16 are eiectively interacted with theA cracked products of the gas oil stock. The gasoline produced in an operation of this type will have an octane number of about Q. F. R. by the motor method. In the cracking of gas-oil type stock alone in the reaction heater it with the same type catalyst mixture the octane number ofthe gasoline ils-slightly lower or about 3l.

when it a desires to convert iight marrocaibons or constituents such as C3 and Cr, these materials may be supplied exclusively through lines 16 and 18 or they may be divided so that s'ome of the feed stock is supplied through the line 2. Butylene and isobutylene may be subjected to polymerization or used for alkylation reactions with parafilns directly in the furnace y'96, and the resulting products passed directly to the absorber 46 or inter-reacted with other exception of the light hydrocarbons from receiver 1I may be fresh straight run charging stocks introduced through lines 2 or 1B. Kero` serie or gas oil type stocks may of course be supplied through lines I2 or 48 or both and recovered in the tower il! so that they will be in fact supplied to the pipe still heater 6 through the line 4.

The activated carbon catalyst `used in the process may be obtained from any source and may comprise powdered activated charcoal or some of the carbon which may be produced in the conversion operation after activation. The inorganicy catalyst which is preferably of the clay type may be products commonly known as bauxite, Florida clay, natural aluminum hydrosilicates,V fullers earth, and similar materials whichlare activated, but which may contain a very small percentage of combined water. Ac-

tivation of such materials with humid air or air and steam at fairly high temperatures appears to produce an inorganic material of an acidic nature which promotes alkylation and polymerization reactions. The catalyst mixture should comprise about %`by-weight of activated carbon to be fully eifective.

While the nature of the action of the activated mixed catalyst is not definitely known, one explanation involves the idea that the activated carbon in the presence of the clay dehydrogenates paraillnic hydrocarbons and promotes cracking or cleavage where the chain is long, while at the same time the newly formed hydrogen ions produced from the hydrogen ofthe dehydrogenation, in the presence of the clay and carbon catalysts activate the oleflns, such as the C3 and C4 hydrocarbons. and promote their polymerizations to form dimers which may be hydrogenated directly by the hydrogen 4produced in the reaction. The activated clay type catalyst furthermore promotes the alkylation re- 1. The process of catalytically converting hydrocarbon oils, which comprises mingling a hydrocarbonoil distillate with approximately an equal weight ci powdered catalytic materials comprising a mixture of approximately of activated carbon and approximately 80% of active inorganic clay type catalytic material, passing the mixture of hydrocarbon distillate and catalytic materials through a reaction zone in. which the mixture is subjected to a temperature of from 860 F. to 970 F. to eifect dehyactions especially in conjunction with the activated carbon which aids in the shifting of the hydrogen from the saturated hydrocarbon to be alkylated. InI the production of hydrogen ions as referred to above, and the activation of olens, it may be that the oleiln is activated by the hydrogen ions to form a complex. In any case the catalyst mixture containing a substantial percentage of activated carbon is very effective drogenation, alkylation and polymerization reactions and produce a substantial proportion of constituents boiling in the gasoline range which are of relatively high antiknock value, passing the mixture of reaction products and catalytic materials into a separating zone in which the catalytic materials are separated from the reaction products, recovering the gasoline range materials from the reaction products, separating the catalytic materials removed from said reaction products into a carbon fraction and an inorganic fraction, separately regenerating said fractions for reuse in the process, mingling the regenerated catalytic materials with a light hydrocarbon distillate containing substantial proportions of oleilns, heating the resulting mixture to a temperature approximating the reaction temperature and cycling the resulting heated mixture through the reaction zone with the distillate charging stock` passed .therethrough to supply the catalytic materials for the conversion of said distillate charging' stock and said light distillate to constituents boiling in the gasoline range.

2. The process as defined by claim 1 in which the reaction products are recovered at low pressure, cooled to substantially atmospheric temperature and passed into the lower portion of a low pressure absorber in which C: and lower gases are eliminated and Ca and higher molecular weight 4constituents are recovered in a rich absorption medium, and separating C: and C4 hydrocarbons from said medium to supply at least in part said light hydrocarbon distillate.

drocarbon oils, which comprises mingling a hydrocarbon oil distillate with approximately an equal weight of powdered catalytic materials comprising a mixture of from 10 to 40% of activated carbon and from to 60% ofactive inorganic clay type catalytic material, passing the mixture of hydrocarbon distillate and suspended catalytic materials through a reaction zone in which the mixture is subjected to a reaction temperature adapted to effect dehydrogenation, alkylation and polymerization reactions and produce a substantial proportion of constituents boiling in the gasoline range which are of relatively high antiknock value, passing the mixture of reaction products and catalytic materials into a separating zone in which thecatalytic materials are separated from the reaction products, recovering the gasoline range materials from the reaction products, separating the catalytic materials removed from said reaction products into a carbon fraction and an inorganic fraction, separately regenerating said fractions for reuse in the process, and returning the regenerated catallyst fractions to the process with additional hytial proportion of a mixture of powdered catalytic materials comprising from to 40% of activated carbon and from 90% to 60% of an inorganic active catalyst of the clay type, conducting the conversion reaction in a reaction Zone in which the hydrocarbon distillate is converted at a temperature of from 860 F. to 970 F. by a combination of reactions including dehydrogenation, alkylation and polymerization by which a substantial proportion of constituents boiling in the gasoline range and having relatively high antiknock properties are produced, passing the mixture of reaction products from the reaction zone, and recovering the constituents boiling in the gasoline range from the reaction products.

5. A process as denedvby claim 4 in which the mixture of catalytic materials is supplied to the reaction zone in suspension in a light hydrocarbon vapor comprising C; and C4 hydrocarbons which enter into the reaction in said zone.

6. In a process for the conversionvof hydrocarbon oils in which a hydrocarbon distillate 'is converted by reacting the distillate with a solid conversion catalyst, the improvement which comprises reacting the hydrocarbon oil distillate to be separated from the reaction products. recovering the constituents boiling in the gasoline range' from .the reaction products. separating the carbon catalyst from the inorganic catalyst of the catalyst materials'separated from the reaction products and separately regenerating them, and returning the separately regenerated catalysts to the reaction zone. v

7. In a continuous process for the conversion of hydrocarbon oils inwhich a hydrocarbon distillate is'converted by reacting the distillate with a solid conversion catalyst, the improvement which comprises reacting the hydrocarbonv oil distillate to be converted with a substantial proportion of a finely divided solid catalytic material comprising a mixture consisting mostly of lan inorganic active catalyst of the clay type and a substantial proportion of activated carbon by passing the hydrocarbon distillate together with the finely divided catalytic mixture through a reaction zone maintained at a relatively low pressure in which the hydrocarbon distillate is cont verted in contact with the catalytic mixture at a converted with a substantial proportion of a ilnely divided solid catalytic material comprising a mixture consisting mostly of an inorganic active catalyst of the clay type and a substantial proportion of activated carbon by passing the hydrocarbon distillate together with thevfinely divided catalytic mixture through a reaction zone in which the hydrocarbon distillate is converted in contact with the catalytic mixture at a reaction temperature adapted to eiect conversion of the distillate into a reaction product containing -a substantial proportion of constituents boiling in reactionv temperature of from"885 to 970 F.

adapted to effect conversion of the distillate into a reaction product containing a substantial proportion of constituents boiling in the -gasoline range and having relatively high antiknock properties, passing the mixture of reaction products` .5 and catalytic materials into a separating zone in which the catalytic materials are separated from the' reaction products, recovering the constituents boiling in the gasoline range from the reaction products, separating thel carbon catalyst from the inorganic catalyst of the catalyst materials separated from. the reaction products and separatelyvregeneratmg them, and returning the the gasoline range and having relatively high antiknock properties. passing the mixture of reac tion products and catalytic materials into a separating zone in which the catalytic materials are separately regenerated catalysts to the reaction zone. A

' ARNOLD R. WORKMAN. 

